US5478641A - Latex containing copolymers having a plurality of activatable functional ester groups therein - Google Patents

Latex containing copolymers having a plurality of activatable functional ester groups therein Download PDF

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US5478641A
US5478641A US07/150,601 US15060188A US5478641A US 5478641 A US5478641 A US 5478641A US 15060188 A US15060188 A US 15060188A US 5478641 A US5478641 A US 5478641A
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vinyl
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Walter A. Schmeing
Woodrow W. White
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Omnova Services Inc
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Gencorp Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Definitions

  • the present invention relates to copolymers made from latex type monomers and effective amounts of functional type monomers including a monomer containing an activatable ester group.
  • the present invention further relates to cured latexes thereof.
  • U.S. Pat. No. 3,422,139 to Talet, et al relates to acrylamido-N-glycolic acids as well as N-methylol-acrylamido-N-glycolic acids and their use in treatment of paper.
  • European Patent Application No. 20,000 relates to ethylenically unsaturated monomers containing activated ester groups which are used to make polymers and copolymers useful in coatings, adhesives, and the like.
  • U.S. Pat. No. 4,254,003 to Fox relates to an aqueous dispersion of polymer particles wherein the polymer comprises both a) polar groups such as amine and ureido groups and b) poly(alkylene oxide) chains covalently bonded to the polymer.
  • polar groups such as amine and ureido groups
  • poly(alkylene oxide) chains covalently bonded to the polymer.
  • U.S. Pat. No. 4,443,623 to Photis relates to the preparation of methyl acrylamidoglycolate methyl ether and a normally liquid product.
  • U.S. Pat. No. 4,522,973 to Ley relates to a low temperature crosslinkable emulsion containing a crosslinkage polymer derived from an activated ester-containing vinyl monomer and including a crosslinking agent having a plurality of groups therein each capable of low temperature reaction with the activated ester group.
  • a cured emulsion copolymer comprises the cured emulsion copolymer, said copolymer made from an effective amount of at least one latex forming monomer and two or more functional type monomers, wherein at least one of said functional type monomers has a vinyl group therein as well as an activatable ester group, and wherein at least one of said functional type monomers are the various acrylamides, the various methacrylamides, the various vinyl ethers, the various non-saturated mono or dicarboxylic acid, or combinations thereof.
  • FIG. 1 is a chart of the wet tensile strength utilizing MAGME and acrylic acid as set forth in Example 1.
  • FIG. 2 is a chart of the wet tensile strength utilizing MAGME and acrylamide as set forth in Example 2.
  • the copolymers of the present invention are suitable for use as aqueous dispersions or as latexes, as well as for various applications thereof.
  • the functionalized copolymer of the present invention that is, the emulsion copolymer is made from one or more latex forming monomers and two or more functional type monomers wherein at least one of said functional type monomers has an activatable ester group. Accordingly, the amount of the different types of monomers utilized, for example the latex forming monomers, will be based upon 100 parts by weight of the total monomers (PHM) utilized in forming the functionalized copolymer of the present invention. It is thus to be understood that hereinafter “total monomer” refers to all of the monomers, that is the latex forming monomers and the two or more functional type monomers utilized in forming the functionalized copolymer of the present invention.
  • the latex forming monomers are known to the art and to the literature.
  • One suitable class of latex forming monomers are the various conjugated dienes.
  • a suitable latex forming copolymer thereof is made with either another conjugated diene monomer or preferably a vinyl substituted aromatic monomer.
  • the amount thereof is from about 1% to about 99% by weight based upon the total monomers utilized in forming the functionalized copolymer of the present invention.
  • the percentage description will be utilized hereinafter.
  • a vinyl substituted aromatic comonomer is utilized, the amount thereof is from about 0% or 1% to about 70% and preferably from about 40% to about 65% by weight based upon the weight of the total monomers.
  • conjugated diene monomers they generally have from about 4 to 8 carbon atoms and desirably from 4 to 6 carbon atoms.
  • specific diene monomers include piperylene, isoprene, 2,3-dimethyl-1,3-butadiene, and preferably 1,3-butadiene. Mixtures of these various conjugated dienes can also be utilized.
  • vinyl substituted aromatic monomers which can be utilized in association with the conjugated dishes to form copolymers, generally they have from 8 to about 12 total carbon atoms.
  • Such monomers include alpha methyl styrene, p-tertiary butyl styrene, methyl vinyl toluene, p-vinyl toluene, 3-ethyl styrene, and the like with styrene being preferred.
  • Mixtures of such vinyl substituted aromatic monomers can also be utilized.
  • acrylonitrile monomers various derivatives thereof can be utilized such as methacrylonitrile, fumaronitrile, and the like.
  • Suitable class of latex forming monomers are the various vinyl esters.
  • the vinyl esters usually yield very high glass transition temperature polymers, conventional amounts of plasticizers are generally utilized therewith such as dioctyl phthalate, or they are copolymerized with various comonomers.
  • Suitable vinyl esters include monomers wherein the ester portion of the vinyl esters is desirably an alkyl having from 1 to 8 carbon atoms.
  • a preferred vinyl ester is vinyl acetate.
  • suitable comonomers include ethylene, and esters of various mono or dicarboxylic acids.
  • a latex forming copolymer is made from monomers of vinyl esters and ethylene
  • the amount of ethylene is from about 10% to about 95% by weight based upon the weight of the total monomers.
  • latex forming copolymers are made from vinyl ester monomers and the esters of mono or dicarboxylic acid
  • the amount of the mono or dicarboxylic acid esters is also from about 5% to about 50% by weight and desirably from about 15% to about 25% by weight based upon the weight of the total monomers.
  • esters of dicarboxylic acids which can be utilized as comonomers with the vinyl esters, they are generally esters of dicarboxylic acids having from 2 to 12 carbon atoms and desirably from 4 to 8 carbon atoms. Examples of such specific esters include diethyl fumarate, dibutyl fumarate, and diethyl maleate, and dibutyl maleate.
  • ethylene monomers are generally always utilized in the form of a copolymer. Suitable latex forming copolymers are thus made utilizing ethylene and vinyl chloride or various vinyl ester monomers.
  • the amount of vinyl chloride monomers utilized with ethylene is from about 5% to about 40% by weight based upon the weight of the total monomers.
  • the amount of the vinyl esters utilized with the ethylene is from about 5 to about 90% by weight.
  • the various types of vinyl ester monomers which can be utilized to form copolymers with the ethylene monomers are as set forth hereinabove.
  • the various latex forming monomers generally form the bulk of the emulsion copolymer, that is from about 85% to about 99.5%, desirably from about 90% to about 99%, and preferably from about 94% to about 97% by weight based upon the weight of the total monomers, it is an essential aspect of the present invention to utilize two or more different types of functional monomers.
  • a type of functional monomer which is always utilized in the present invention is characterized by having at least one vinyl group therein which is polymerizable and at least one activatable ester group which enables the copolymer to be cured or crosslinked; hereinafter referred to as an activatable ester monomer.
  • the various activatable ester monomers include:
  • MAGME methyl acrylamidoglycolate methyl ether
  • the functional containing monomer contains an activatable acid group thereon
  • specific examples of such compounds are acid derivatives of the above compounds, for example acrylamidoglycolic acid, and the like.
  • the second or additional type of other functional monomers which are optionally utilized include anionic monomers such as, the various acrylamides, the various methacrylamides, the various vinyl ethers, and the various non-saturated mono-or dicarboxylic acids.
  • anionic monomers such as, the various acrylamides, the various methacrylamides, the various vinyl ethers, and the various non-saturated mono-or dicarboxylic acids.
  • cationic monomers can be utilized as set forth hereinbelow.
  • the total amount of such monomers including the activatable ester functional monomers is generally small as from about 0.5% to about 15% by weight, desirably from about 1 to about 10% by weight and preferably from about 3% to about 6% by weight based upon the weight of the total monomers.
  • the acrylamides and the methacrylamides include various alkyl derivatives thereof having from 1 to 2 carbon atoms attached to either the nitrogen atom and/or the vinyl group with specific examples including dimethylacrylamide, methylene bisacrylamtde, and the like.
  • the vinyl ethers are another class of vinyl type monomers which can be utilized in the present invention. They are generally represented by the formula ##STR1## wherein;
  • R' is an alkyl group having from 1 to 6 carbon atoms, or a substituted chloroalkyl group having a total of from 1 to 6 carbon atoms.
  • Examples of such specific vinyl ethers include n-butyl vinyl ether, vinyl chloroethyl ethyl, and the like.
  • the acids which are utilized are an unsaturated monocarboxylic or a dicarboxylic acid monomer containing a total of from 3 to about 8 carbon atoms and preferably from to about 5 carbon atoms.
  • monocarboxylic acids include acrylic acid and methacrylic acid.
  • dicarboxylic acids include fumaric acid, maleic acid, taconic acid, and the like. Itaconic acid is preferred.
  • the amount of the acrylamides, the methacrylamides, the vinyl ethers, or the mono or dicarboxylic acid monomers, or combinations thereof generally range from about 0.5% to about 5% by weight and preferably from about 1% to about 3% by weight based upon the weight of the total monomer.
  • the amount of activatable ester can be from about 1 to about 10% with the amount of the second functional monomer being from about 0.5 to about 5% thereby achieving the overall range of from about 0.5% to about 15% by weight of functional monomers.
  • copolymer forming monomers of the present invention that Is the primary and the optional secondary latex forming monomers, and the two or more functional type monomers are reacted according to any conventional free radical aqueous emulsion polymerization method known to the art as well as to the literature to form the emulsion type copolymer of the present invention.
  • Any conventional free radical aqueous emulsion polymerization method known to the art as well as to the literature to form the emulsion type copolymer of the present invention are discussed herein below.
  • emulsion polymerization additives include various emulsifiers, various chain transfer agents or extenders which act as molecular weight modifiers, various free-radical initiators, various chelating agents, various shortstops, electrolytes, and the like.
  • emulsifiers they can be any compound well known to the art as well as to the literature such as soaps, surfactants, dispersing agents, and the like which are stable at low pH, e.g. 1.5 to 3.5.
  • the surfactants, as well as the other emulsifiers can be cationic, anionic, or mixtures thereof with nonionics.
  • Examples of specific emulsifiers include the various alkyl sulfates, the various alkyl sulfosuccinates, the various alkyl aryl sulfonates, the various alpha olefin sulfonates, the various quaternary ammonium salt, the various amine salts, the various fatty or resin acid salts, nonyl or octyl phenol reaction products of ethylene oxide and the like.
  • the alkyl portion of the various emulsifiers generally has from 8 to 18 carbon atoms. Naturally, an amount of an emulsifier is utilized to obtain an aqueous emulsion of the various monomers.
  • such an amount is typically from about 0.5 to about 5 or 6 parts by weight for every 100 parts by weight of the monomers.
  • Other surfactants can be utilized such as those set forth in "Surface Active Agents,” Schwartz and Perry, Vol. I, Interscience Publishers, Inc., New York, 1958; "Surface Activity,” Motliter, Collie and Black, D. Van Nostrand Company, Inc., New York, 1961; “Organic Chemistry,” Fieset and Fieset, D. C. Heath and Company, Boston, 1944; and "The Merck Index,” Seventh Edition, Merck & Co., Inc., Rahway, N.J., 1960, all of which are hereby fully incorporated by reference.
  • the various chain extenders or molecular weight regulators can be conventional compounds as well as those known to the art and to the literature. Accordingly, compounds such as benzene, toluene, triphenyl methane, and carbon tetrachloride can be utilized. However, mercaptans such as the alkyl and/or aralkyl mercaptans having from 8 to about 18 carbon atoms and preferably from about 12 to about 14 carbon atoms are preferably utilized. The tertiary alkyl mercaptans having from 12 to 14 carbon atoms are highly preferred.
  • Suitable mercaptans include n-octyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, t-dodecyl mercaptan, p-tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, and the like, as well as mixtures thereof.
  • the amount of the molecular weight modifiers is an effective amount to provide for the proper retention of the tensile strength of the interpolymer, for example from about 0.1 to about 5.0 parts by weight and desirably from about 0.2 to about 1.0 parts by weight for every 100 parts by weight of the monomers.
  • Free-radical initiators are utilized to polymerize the various monomers and are utilized in amounts sufficient to obtain a desired molecular weight. A suitable amount is generally from about 0.25 to about 2.0 with from about 0.5 to about 1.5 parts being preferred for every 100 parts by weight of the monomers.
  • Conventional free-radical initiators can be utilized as well as those known to the art and to the literature. Specific examples include ammonium persulfate, potassium persulfate, or or sodium persulfate, hydrogen peroxide, and the like. Other free-radical initiators can be utilized which decompose or become active at the temperature utilized during polymerization.
  • Examples of other free-radical catalysts include cumene hydroperoxide, dibenzoyl peroxide, diacetyl peroxide, dodecanoyl peroxide, di-t-butyl peroxide, dilauoyl peroxide, bis(p-methoxy benzoyl) peroxide, t-butyl peroxy pivalate, dicumy/peroxide, isopropyl percarbonate, di-sec-butyl peroxidicarbonate, azobisdimethylvaleronitrile, 2,2'-azobtsisobutyronitrile, 2,2'-azobis-2-methyl-butyronitrile, 2,2'-azobis (methylisobutyrate) and the like and mixtures thereof.
  • inorganic persulfates of which the sodium salt is preferred since they impart better color to the resulting polymer when dried.
  • Organic hydroperoxides such as t-butyl hydroperoxides are preferred for the cationic system of the present invention.
  • Chelating agents can be utilized during polymerization to tie up various metal impurities as well as to achieve a uniform polymerization.
  • the amounts of such chelating agents are generally small such as from about 0.01 to about 0.25 parts by weight for every 100 parts by weight of the monomers.
  • suitable chelating agents include ethylene diamine tetraacetic acid, nitrilotriacetic acid, citric acid, and their ammonium, potassium, and sodium salts.
  • shortstop compounds can also be utilized. Not only do the shortstop compounds terminate the polymerization in the reactor at desired conversion levels, but also prevent further polymerization, crosslinking, etc., during stripping, and the like.
  • suitable shortshop agents include hydroquinone, sodium sulfide, hydroxyl ammonium acid sulfate, hydroxyl ammonium sulfate, sodium diethyl dithiocarbamate, diethylhydroxylamine, sodium dimethyl dithiocarbamate, potassium dimethyl dithiocarbamate, dimethylammonium dimethyldithiocarbamate, hydroxylamine sulfate plus sodium hydrosulfite, and the like.
  • the amount of shortshop utilized is from about 0.05 to about 0.25 parts by weight for every 100 parts by weight of said monomers.
  • other conventional chelating agents as well as shortstops can be utilized including those known to the art and to the literature.
  • the electrolytes are generally neutral such as the various sulfates, and various monobasic salts thereof. These and other electrolytes are known to the art as well as to the literature.
  • the amount of such electrolytes can generally be from about 0.05 to about 1.0 and preferably from about 0.05 to about 0.75 parts by weight for every 100 parts by weight of said monomers.
  • Suitable cationic monomers include the dimethyl sulfate quaternized product of dimethyl amino ethyl methacrylate, the methyl chloride quarternized product of dimethyl amino ethyl methacrylate, methacryl amino propyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, N(3-chloro-2-hydroxy propyl)trimethyl ammonium chloride, 2-hydroxy-3-methacryloyloxy propyl trimethyl ammonium chloride, and the amine monomers dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, tertiary butyl amino ethyl methacrylate and dimethyl amino propyl methacrylamide.
  • cationic type surfactants are very desirable.
  • the preparation of the copolymers made from such cationic functional monomers differs in that cationic additives are utilized including various cationic chain transfer agents or extenders, various cationic initiators, various cationic chelating agents, various cationic shortstops, and the like. Otherwise, preparation proceeds in a manner as noted above, for example the cationic monomers are free radically polymerized.
  • Polymerization of the various monomers is carried out at a temperature sufficient to activate the initiators and the double bonds of the monomers. However, extremely high temperatures are avoided since they cause a run-away reaction. Too low temperatures are not desired since they retard polymerization. Suitable polymerization temperatures are from about 2° C. to about 90° C., desirably from about 35° C. to about 80° C., and preferably from about 85° C. to about 77° C. Polymerization time will naturally vary depending upon the type of monomers utilized, the type of initiator utilized, and the degree of polymerization desired. Hence, typical polymerization times can range from about 5 to about 35 hours. Polymerization is generally carried out to completion and conducted in an acidic medium when acidic monomers are utilized.
  • optional bases can be added to neutralise the latex.
  • optional bases include NaOH, KOH, NH 4 OH, and the like.
  • an acidic latex is desired having a pH of from about 2.0 to 7.0 and desirably from about 2.0 to about 4.0.
  • the free radical polymerization can be carried out according to any conventional method including batch, incremental, or continuous.
  • the water used during the polymerization should be free of deleterious material and hence is often distilled or ion exchanged water.
  • the amount of water used is sufficient to enable the formation of an emulsion and to enable proper mixing of the various ingredients as well as to obtain the desired rate and degree of polymerization, heat transfer, and the like.
  • the amount of copolymer or solids content can vary from about 10% to about 60% by weight and preferably from about 40% to about 55% by weight.
  • Desirably polymerization is conducted in an inert atmosphere such as nitrogen, helium, argon, and the like and hence it is carried out in a closed reactor.
  • the reactor can be any conventional reactor and thus have suitable ports, agitation means, heating and cooling means, and the like.
  • the reactors utilized are generally cleaned as by flushing with water between polymertzations to remove traces of various initiators, shortstops, residues, surfactants, and the like.
  • copolymer latexes of the present invention can be treated with other conventional additives such as antioxidants, biocides, defoamers, and the like as known to the art and to the literature.
  • the latexes of the present invention can be compounded with various finely divided fillers such as various paper coating fillers, for example clays, kaolin, calcium carbonate, titanium dioxide, zinc oxide and other inorganic fillers commonly used in the paper coating compositions.
  • various paper coating fillers for example clays, kaolin, calcium carbonate, titanium dioxide, zinc oxide and other inorganic fillers commonly used in the paper coating compositions.
  • Various thickening agents, viscosity stabilizers, and the like can also be utilized.
  • the latexes of the present invention can be utilized on various cellulosic materials such as paper, for example paper towels, coated paper, masking tapes, label tapes, containers, or the like. They can be applied in any conventional manner such as by spraying, by saturation, e.g. dipping the paper into the latex, by coating, and the like.
  • the latexes can further be applied to variously formed materials, be they paper, synthetic fibers such as polyesters, polypropylenes, rayon, nylons, to masking tapes, to carpets, and the like. Another desired area of use is on various nonwoven textiles.
  • mats various hospital disposable products such as face masks, gowns, gloves, and the like, as well as commercial applications wherever mats are utilized such as in diapers, and the like.
  • a preferred use is in the application of paper since it has been found that the latexes of the present invention unexpectedly improved cure rate development.
  • the latexes of the present invention can be cured. Curing generally occurs by heating at a temperature of from about 25° C. to about 180° C. and preferably from about 100° C. to about 150° C. Curing can occur as in the presence of a heating means, for example an oven, an electronbeam, infrared heat, or at ambient temperature, or the like.
  • a heating means for example an oven, an electronbeam, infrared heat, or at ambient temperature, or the like.
  • the use of two functional monomers that is an activatable ester monomer and either an acrylamide type monomer, a methacrylamide type monomer, a vinyl ether type monomer, or a carboxylic acid type monomer, or combinations thereof, has been found to generally result in a quicker cure time and/or a lower cure temperature when utilized with the various latex monomers. This is desirable since quicker or faster crosslinking times are useful.
  • the initial cure strength that is the wet tensile strength
  • a second functional containing monomer for example acrylic acid.
  • Cure time is very important in the utilization of latexes in that short heating times are highly desirable. For example, in the application of coatings to cellulosic material such as towels, quick cure times are desired.
  • Example 1 as well as FIG. 2, also reveals that improved wet strengths are obtained utilizing a second functional monomer. That is at all cure times, large absolute improvement values in the wet tensile strength are obtained.
  • Example 2 as well as FIG. 2, it is once again apparent that utilization of a second functional monomer such as acrylamide yields great improvements in the initial cure time, that is the initial slope of the various curves. More importantly, as set forth in Example 2, dramatic improvements in the wet tensile strength are obtained and thereby conclusively proving that a synergistic result is obtained.
  • use of the second or more functional type monomers results in an absolute value increase in the wet tensile strength at generally any given cure time. For example,.at 300 seconds of at least 1.5, desirably 2.0, and preferably 2.5 lbs/in.
  • test method utilized in the examples for measuring wet tensile strength is as follows:
  • Whatman #4 chromatographic paper die-cut to 8" ⁇ 10" is used with a tolerance of ⁇ 5.0% in an untreated weight basis.
  • the sheets are saturated with the latex using a laboratory padder at a binder add-on target of 20 ⁇ 1.5% based on the finished sheet weight.
  • the saturated sheets are air dried at room temperature and then duplicate sheets are cured on the steam heated drier cans at 315° F. for 15, 30, 60, and 300 seconds. All sheets are conditioned in accordance with TAPPI test method T402 before testing. Then they are immersed in distilled water until they are completely wetted.
  • the tensile is then determined on four test strips in both the machine direction (MD) and in the cross direction (CD) for each cured sheet. The average of the eight results in each direction and the total tensile is reported as the sum of the CD and MD averages. This result is normalized to a basic weight of 73.0 lbs./300 ft. and a binder add on of 20%.
  • Bottle scale polymertzations were carried out using the ingredients set forth below. In each case an initial charge was made to the bottles using the ingredients in the order listed in the table. The bottles were flushed with nitrogen, capped, and allowed to react 45 minutes at 65° C.
  • the bottles were opened, recharged with the appropriate amount of styrene, Sulfole 120 and butadiene, as listed in the table. This charge was reacted until the bottles were under vacuum as a result of most of the monomers having reacted.
  • the bottles were opened a second time and further monomers, Sulfole 120, MAGME, and other cofunctional monomers added, as listed. This charge was also reacted to vacuum.
  • the latexes obtained were tested without stripping. Some latexes were tested at the pH of the finished latex while others were tested at a pH of about 7.5 after adjustment with ammonium hydroxide.
  • Latexes A and B of the bottle scale series relate to the use of MAGME in combination with acrylic acid and the use of itaconic acid in the initial step. These latexes both had 5 parts of MAGME and 0 and 2 parts respectively of acrylic acid.
  • Latex B was also tested at 2.5 pH before adjustment. Results for total wet tensile strength were as follows:
  • Latex B which contains both acrylic acid and MAGME is better than Latex A which contains only MAGME. Not only did both "B" examples have a faster cure rate, but a higher wet tensile strength was also obtained. Thus, synergistic results were obtained.
  • Latexes C, D, E, and F of the bottle series illustrate the, use of acrylamide with MAGME and the synergistic effect thereof.
  • Test results for total wet tensiles of Whatman #4 paper saturated with these latexes at low pH are as follows:
  • This example relates to the fact that a single anionic surfactant, Aerosol MA, can also be used to produce latexes.
  • the latexes were prepared in bottles using 0.78 PHM of Aerosol MA-80 as the only surfactant.
  • This example relates to the preparation of latexes in bottles using a cationic system.
  • the ingredients and latex properties are set forth in the following table:

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Abstract

An aqueous latex contains a functionalized copolymer prepared by emulsion polymerization. The copolymer can be applied to textile nonwoven materials and to various cellulosic substrates, and when utilized as a binder imparts enhanced properties thereto such as wet tensile strength, low temperature cure rates, and the like. The monomers generally forming the copolymer include at least two functional type monomers, one of which contains an activatable ester group, and at least one latex forming monomer.

Description

CROSS REFERENCE
This application is a division of application Ser. No. 07/025,249 filed Mar. 12, 1987, now U.S. Pat. No. 4,808,660, which is a continuation-in-part of U.S. application Ser. No. 06/848,018 filed Apr. 3, 1986, now abandoned, for "Latexes Containing Copolymers Having Functional Groups Therein."
FIELD OF THE INVENTION
The present invention relates to copolymers made from latex type monomers and effective amounts of functional type monomers including a monomer containing an activatable ester group. The present invention further relates to cured latexes thereof.
PRIOR ART
A series of articles, namely, Polymer Journal Volume 5, pages 186-194 (1973); Volume 6, pages 412-418 (1974); Volume 7, pages 72-78 (1975) and Volume 10, pages 499-504 (1978), by Ogata, et al, generally relate to beta-hereto atom containing diesters or dibasic acids which react under mild conditions with amines to form polyamides.
U.S. Pat. No. 3,422,139 to Talet, et al, relates to acrylamido-N-glycolic acids as well as N-methylol-acrylamido-N-glycolic acids and their use in treatment of paper.
European Patent Application No. 20,000 relates to ethylenically unsaturated monomers containing activated ester groups which are used to make polymers and copolymers useful in coatings, adhesives, and the like.
U.S. Pat. No. 4,254,003 to Fox relates to an aqueous dispersion of polymer particles wherein the polymer comprises both a) polar groups such as amine and ureido groups and b) poly(alkylene oxide) chains covalently bonded to the polymer. such dispersed polymers are useful in latex paint compositions.
U.S. Pat. No. 4,443,623 to Photis relates to the preparation of methyl acrylamidoglycolate methyl ether and a normally liquid product.
U.S. Pat. No. 4,522,973 to Ley relates to a low temperature crosslinkable emulsion containing a crosslinkage polymer derived from an activated ester-containing vinyl monomer and including a crosslinking agent having a plurality of groups therein each capable of low temperature reaction with the activated ester group.
The above documents do not disclose the polymerization of the various comonomers in an aqueous latex or the various unexpected physical properties obtained when a plurality of functional type monomers having at least one monomer containing an activatable ester group therein is utilized at the levels employed in the present invention.
SUMMARY OF THE INVENTION
Accordingly, it is an aspect of the present invention to provide a latex type copolymer prepared by emulsion polymerization containing an activatable ester group.
It is another aspect of the present invention to provide a latex type copolymer, as above, made from monomers forming a latex emulsion as well as from a plurality of functional monomers, one of which has a polymerizable vinyl group and an activatable crosslinking ester group.
It is yet a further aspect of the present invention to provide a latex type copolymer, as above, which when applied to nonwoven textile and cellulosic substrates generally yields improved end use properties and cure rates.
It is still another aspect of the present invention to provide a latex type copolymer, as above, which has improved wet strength upon cure.
These and other aspects of the present invention will become apparent from the following detailed specification.
In general, a cured emulsion copolymer, comprises the cured emulsion copolymer, said copolymer made from an effective amount of at least one latex forming monomer and two or more functional type monomers, wherein at least one of said functional type monomers has a vinyl group therein as well as an activatable ester group, and wherein at least one of said functional type monomers are the various acrylamides, the various methacrylamides, the various vinyl ethers, the various non-saturated mono or dicarboxylic acid, or combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a chart of the wet tensile strength utilizing MAGME and acrylic acid as set forth in Example 1.
FIG. 2 is a chart of the wet tensile strength utilizing MAGME and acrylamide as set forth in Example 2.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
The copolymers of the present invention are suitable for use as aqueous dispersions or as latexes, as well as for various applications thereof. The functionalized copolymer of the present invention, that is, the emulsion copolymer is made from one or more latex forming monomers and two or more functional type monomers wherein at least one of said functional type monomers has an activatable ester group. Accordingly, the amount of the different types of monomers utilized, for example the latex forming monomers, will be based upon 100 parts by weight of the total monomers (PHM) utilized in forming the functionalized copolymer of the present invention. It is thus to be understood that hereinafter "total monomer" refers to all of the monomers, that is the latex forming monomers and the two or more functional type monomers utilized in forming the functionalized copolymer of the present invention.
The latex forming monomers are known to the art and to the literature. One suitable class of latex forming monomers are the various conjugated dienes. A suitable latex forming copolymer thereof is made with either another conjugated diene monomer or preferably a vinyl substituted aromatic monomer. When a conjugated diene comonomers is utilized, the amount thereof is from about 1% to about 99% by weight based upon the total monomers utilized in forming the functionalized copolymer of the present invention. Generally, the percentage description will be utilized hereinafter. When a vinyl substituted aromatic comonomer is utilized, the amount thereof is from about 0% or 1% to about 70% and preferably from about 40% to about 65% by weight based upon the weight of the total monomers.
Considering the conjugated diene monomers, they generally have from about 4 to 8 carbon atoms and desirably from 4 to 6 carbon atoms. Examples of specific diene monomers include piperylene, isoprene, 2,3-dimethyl-1,3-butadiene, and preferably 1,3-butadiene. Mixtures of these various conjugated dienes can also be utilized. Considering the vinyl substituted aromatic monomers which can be utilized in association with the conjugated dishes to form copolymers, generally they have from 8 to about 12 total carbon atoms. Specific examples of such monomers include alpha methyl styrene, p-tertiary butyl styrene, methyl vinyl toluene, p-vinyl toluene, 3-ethyl styrene, and the like with styrene being preferred. Mixtures of such vinyl substituted aromatic monomers can also be utilized. Considering the acrylonitrile monomers, various derivatives thereof can be utilized such as methacrylonitrile, fumaronitrile, and the like.
Yet another suitable class of latex forming monomers are the various vinyl esters. Inasmuch as the vinyl esters usually yield very high glass transition temperature polymers, conventional amounts of plasticizers are generally utilized therewith such as dioctyl phthalate, or they are copolymerized with various comonomers. Suitable vinyl esters include monomers wherein the ester portion of the vinyl esters is desirably an alkyl having from 1 to 8 carbon atoms. A preferred vinyl ester is vinyl acetate. Examples of suitable comonomers include ethylene, and esters of various mono or dicarboxylic acids. When a latex forming copolymer is made from monomers of vinyl esters and ethylene, the amount of ethylene is from about 10% to about 95% by weight based upon the weight of the total monomers. When latex forming copolymers are made from vinyl ester monomers and the esters of mono or dicarboxylic acid, the amount of the mono or dicarboxylic acid esters is also from about 5% to about 50% by weight and desirably from about 15% to about 25% by weight based upon the weight of the total monomers. Considering the various types of esters of dicarboxylic acids which can be utilized as comonomers with the vinyl esters, they are generally esters of dicarboxylic acids having from 2 to 12 carbon atoms and desirably from 4 to 8 carbon atoms. Examples of such specific esters include diethyl fumarate, dibutyl fumarate, and diethyl maleate, and dibutyl maleate.
Yet another class of suitable latex forming monomers-are the ethylene monomers. The ethylenes are generally always utilized in the form of a copolymer. Suitable latex forming copolymers are thus made utilizing ethylene and vinyl chloride or various vinyl ester monomers. The amount of vinyl chloride monomers utilized with ethylene is from about 5% to about 40% by weight based upon the weight of the total monomers. The amount of the vinyl esters utilized with the ethylene is from about 5 to about 90% by weight. The various types of vinyl ester monomers which can be utilized to form copolymers with the ethylene monomers are as set forth hereinabove.
Although the various latex forming monomers generally form the bulk of the emulsion copolymer, that is from about 85% to about 99.5%, desirably from about 90% to about 99%, and preferably from about 94% to about 97% by weight based upon the weight of the total monomers, it is an essential aspect of the present invention to utilize two or more different types of functional monomers. A type of functional monomer which is always utilized in the present invention is characterized by having at least one vinyl group therein which is polymerizable and at least one activatable ester group which enables the copolymer to be cured or crosslinked; hereinafter referred to as an activatable ester monomer. The various activatable ester monomers include:
methyl acrylamidoglycolate (MAG)
ethyl acrylamidoclycolate (EAG)
butyl acrylamidoglycolate (BAG)
methyl acrylamidoglycolate methyl ether (MAGME)
butyl acrylamidoglycolate butyl ether (BAGBE)
methyl methacryloxyacetate
ethyl acrylamido-N-oxalate (N-ethyloxalyl acrylamide)
N,N'-Bis(ethyloxalyl)acrylamide
N-isopropyl, N-ethyloxalyl-3-propylamino methacrylamide
N-ethyloxalyl-N'-methyleneaminoacrylamide
ethyl N-2-ethyloxamatoacrylate
ethyl 3-pyruvylacrylate
ethyl methylenepyruvate
methyl acrylthiocarbonyloxyacetate (Methyl thiacryloxyacetate)
methyl thiacrylthioglycolate
methyl acryl-2-thioglycolate
methyl thiacrylamidoacetate
methyl acrylamidoglycolate thioether
methyl acrylamido-N-methylenethioglycolate
p-ethyl oxalyl styrene,
and the like. Additional examples include the above compounds wherein an alkyl group having from 2 or 3 or 6 carbon atoms can be substituted for the various "methyl", or "ethyl", groups.
When the functional containing monomer contains an activatable acid group thereon, specific examples of such compounds are acid derivatives of the above compounds, for example acrylamidoglycolic acid, and the like.
The second or additional type of other functional monomers which are optionally utilized include anionic monomers such as, the various acrylamides, the various methacrylamides, the various vinyl ethers, and the various non-saturated mono-or dicarboxylic acids. In lieu of these anionic functional monomers, cationic monomers can be utilized as set forth hereinbelow. The total amount of such monomers including the activatable ester functional monomers is generally small as from about 0.5% to about 15% by weight, desirably from about 1 to about 10% by weight and preferably from about 3% to about 6% by weight based upon the weight of the total monomers.
The acrylamides and the methacrylamides include various alkyl derivatives thereof having from 1 to 2 carbon atoms attached to either the nitrogen atom and/or the vinyl group with specific examples including dimethylacrylamide, methylene bisacrylamtde, and the like.
The vinyl ethers are another class of vinyl type monomers which can be utilized in the present invention. They are generally represented by the formula ##STR1## wherein;
R' is an alkyl group having from 1 to 6 carbon atoms, or a substituted chloroalkyl group having a total of from 1 to 6 carbon atoms. Examples of such specific vinyl ethers include n-butyl vinyl ether, vinyl chloroethyl ethyl, and the like.
The acids which are utilized are an unsaturated monocarboxylic or a dicarboxylic acid monomer containing a total of from 3 to about 8 carbon atoms and preferably from to about 5 carbon atoms. Examples of monocarboxylic acids include acrylic acid and methacrylic acid. Examples of dicarboxylic acids include fumaric acid, maleic acid, taconic acid, and the like. Itaconic acid is preferred.
The amount of the acrylamides, the methacrylamides, the vinyl ethers, or the mono or dicarboxylic acid monomers, or combinations thereof generally range from about 0.5% to about 5% by weight and preferably from about 1% to about 3% by weight based upon the weight of the total monomer. Hence, the amount of activatable ester can be from about 1 to about 10% with the amount of the second functional monomer being from about 0.5 to about 5% thereby achieving the overall range of from about 0.5% to about 15% by weight of functional monomers.
The copolymer forming monomers of the present invention, that Is the primary and the optional secondary latex forming monomers, and the two or more functional type monomers are reacted according to any conventional free radical aqueous emulsion polymerization method known to the art as well as to the literature to form the emulsion type copolymer of the present invention. Various copolymerization methods are discussed herein below.
Various conventional amounts of conventional emulsion polymerization additives can also be utilized. Such emulsion polymerization additives include various emulsifiers, various chain transfer agents or extenders which act as molecular weight modifiers, various free-radical initiators, various chelating agents, various shortstops, electrolytes, and the like. Considering the emulsifiers, they can be any compound well known to the art as well as to the literature such as soaps, surfactants, dispersing agents, and the like which are stable at low pH, e.g. 1.5 to 3.5. The surfactants, as well as the other emulsifiers, can be cationic, anionic, or mixtures thereof with nonionics. Examples of specific emulsifiers include the various alkyl sulfates, the various alkyl sulfosuccinates, the various alkyl aryl sulfonates, the various alpha olefin sulfonates, the various quaternary ammonium salt, the various amine salts, the various fatty or resin acid salts, nonyl or octyl phenol reaction products of ethylene oxide and the like. The alkyl portion of the various emulsifiers generally has from 8 to 18 carbon atoms. Naturally, an amount of an emulsifier is utilized to obtain an aqueous emulsion of the various monomers. Generally, such an amount is typically from about 0.5 to about 5 or 6 parts by weight for every 100 parts by weight of the monomers. Other surfactants can be utilized such as those set forth in "Surface Active Agents," Schwartz and Perry, Vol. I, Interscience Publishers, Inc., New York, 1958; "Surface Activity," Motliter, Collie and Black, D. Van Nostrand Company, Inc., New York, 1961; "Organic Chemistry," Fieset and Fieset, D. C. Heath and Company, Boston, 1944; and "The Merck Index," Seventh Edition, Merck & Co., Inc., Rahway, N.J., 1960, all of which are hereby fully incorporated by reference.
The various chain extenders or molecular weight regulators can be conventional compounds as well as those known to the art and to the literature. Accordingly, compounds such as benzene, toluene, triphenyl methane, and carbon tetrachloride can be utilized. However, mercaptans such as the alkyl and/or aralkyl mercaptans having from 8 to about 18 carbon atoms and preferably from about 12 to about 14 carbon atoms are preferably utilized. The tertiary alkyl mercaptans having from 12 to 14 carbon atoms are highly preferred. Examples of suitable mercaptans include n-octyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, t-dodecyl mercaptan, p-tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, and the like, as well as mixtures thereof. The amount of the molecular weight modifiers is an effective amount to provide for the proper retention of the tensile strength of the interpolymer, for example from about 0.1 to about 5.0 parts by weight and desirably from about 0.2 to about 1.0 parts by weight for every 100 parts by weight of the monomers.
Free-radical initiators are utilized to polymerize the various monomers and are utilized in amounts sufficient to obtain a desired molecular weight. A suitable amount is generally from about 0.25 to about 2.0 with from about 0.5 to about 1.5 parts being preferred for every 100 parts by weight of the monomers. Conventional free-radical initiators can be utilized as well as those known to the art and to the literature. Specific examples include ammonium persulfate, potassium persulfate, or or sodium persulfate, hydrogen peroxide, and the like. Other free-radical initiators can be utilized which decompose or become active at the temperature utilized during polymerization. Examples of other free-radical catalysts include cumene hydroperoxide, dibenzoyl peroxide, diacetyl peroxide, dodecanoyl peroxide, di-t-butyl peroxide, dilauoyl peroxide, bis(p-methoxy benzoyl) peroxide, t-butyl peroxy pivalate, dicumy/peroxide, isopropyl percarbonate, di-sec-butyl peroxidicarbonate, azobisdimethylvaleronitrile, 2,2'-azobtsisobutyronitrile, 2,2'-azobis-2-methyl-butyronitrile, 2,2'-azobis (methylisobutyrate) and the like and mixtures thereof. It is preferred to use the inorganic persulfates of which the sodium salt is preferred since they impart better color to the resulting polymer when dried. Organic hydroperoxides such as t-butyl hydroperoxides are preferred for the cationic system of the present invention.
Chelating agents can be utilized during polymerization to tie up various metal impurities as well as to achieve a uniform polymerization. The amounts of such chelating agents are generally small such as from about 0.01 to about 0.25 parts by weight for every 100 parts by weight of the monomers. Examples of suitable chelating agents include ethylene diamine tetraacetic acid, nitrilotriacetic acid, citric acid, and their ammonium, potassium, and sodium salts.
Various shortstop compounds can also be utilized. Not only do the shortstop compounds terminate the polymerization in the reactor at desired conversion levels, but also prevent further polymerization, crosslinking, etc., during stripping, and the like. Examples of suitable shortshop agents include hydroquinone, sodium sulfide, hydroxyl ammonium acid sulfate, hydroxyl ammonium sulfate, sodium diethyl dithiocarbamate, diethylhydroxylamine, sodium dimethyl dithiocarbamate, potassium dimethyl dithiocarbamate, dimethylammonium dimethyldithiocarbamate, hydroxylamine sulfate plus sodium hydrosulfite, and the like. The amount of shortshop utilized is from about 0.05 to about 0.25 parts by weight for every 100 parts by weight of said monomers. Of course, other conventional chelating agents as well as shortstops can be utilized including those known to the art and to the literature.
The electrolytes are generally neutral such as the various sulfates, and various monobasic salts thereof. These and other electrolytes are known to the art as well as to the literature. The amount of such electrolytes can generally be from about 0.05 to about 1.0 and preferably from about 0.05 to about 0.75 parts by weight for every 100 parts by weight of said monomers.
The above description relates to the preparation of an emulsion copolymer utilizing functional monomers which are generally anionic in accordance with the dominant practice of forming aqueous emulsions or latexes. However, it is to be understood that various cationic monomers can be utilized and that such are sometimes an advantage with regard to adhesion to various substrates, and the like. Whenever such cationic monomers are utilized, they are utilized in lieu of the above-noted optional anionic functional monomers. Examples of suitable cationic monomers include the dimethyl sulfate quaternized product of dimethyl amino ethyl methacrylate, the methyl chloride quarternized product of dimethyl amino ethyl methacrylate, methacryl amino propyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, N(3-chloro-2-hydroxy propyl)trimethyl ammonium chloride, 2-hydroxy-3-methacryloyloxy propyl trimethyl ammonium chloride, and the amine monomers dimethyl amino ethyl (meth)acrylate, diethyl amino ethyl (meth)acrylate, tertiary butyl amino ethyl methacrylate and dimethyl amino propyl methacrylamide. When cationic monomers are utilized in lieu of the anionic monomers, cationic type surfactants are very desirable. Moreover, the preparation of the copolymers made from such cationic functional monomers differs in that cationic additives are utilized including various cationic chain transfer agents or extenders, various cationic initiators, various cationic chelating agents, various cationic shortstops, and the like. Otherwise, preparation proceeds in a manner as noted above, for example the cationic monomers are free radically polymerized.
Polymerization of the various monomers is carried out at a temperature sufficient to activate the initiators and the double bonds of the monomers. However, extremely high temperatures are avoided since they cause a run-away reaction. Too low temperatures are not desired since they retard polymerization. Suitable polymerization temperatures are from about 2° C. to about 90° C., desirably from about 35° C. to about 80° C., and preferably from about 85° C. to about 77° C. Polymerization time will naturally vary depending upon the type of monomers utilized, the type of initiator utilized, and the degree of polymerization desired. Hence, typical polymerization times can range from about 5 to about 35 hours. Polymerization is generally carried out to completion and conducted in an acidic medium when acidic monomers are utilized. Upon completion of the reaction or the desired degree of polymerization, optional bases can be added to neutralise the latex. Examples of such optional bases include NaOH, KOH, NH4 OH, and the like. However, an acidic latex is desired having a pH of from about 2.0 to 7.0 and desirably from about 2.0 to about 4.0.
The free radical polymerization can be carried out according to any conventional method including batch, incremental, or continuous. The water used during the polymerization should be free of deleterious material and hence is often distilled or ion exchanged water. The amount of water used is sufficient to enable the formation of an emulsion and to enable proper mixing of the various ingredients as well as to obtain the desired rate and degree of polymerization, heat transfer, and the like. Upon completion of polymerization, the amount of copolymer or solids content can vary from about 10% to about 60% by weight and preferably from about 40% to about 55% by weight.
Desirably polymerization is conducted in an inert atmosphere such as nitrogen, helium, argon, and the like and hence it is carried out in a closed reactor. The reactor can be any conventional reactor and thus have suitable ports, agitation means, heating and cooling means, and the like. In accordance with conventional practice, the reactors utilized are generally cleaned as by flushing with water between polymertzations to remove traces of various initiators, shortstops, residues, surfactants, and the like.
The copolymer latexes of the present invention can be treated with other conventional additives such as antioxidants, biocides, defoamers, and the like as known to the art and to the literature.
The latexes of the present invention can be compounded with various finely divided fillers such as various paper coating fillers, for example clays, kaolin, calcium carbonate, titanium dioxide, zinc oxide and other inorganic fillers commonly used in the paper coating compositions. Various thickening agents, viscosity stabilizers, and the like can also be utilized.
The latexes of the present invention can be utilized on various cellulosic materials such as paper, for example paper towels, coated paper, masking tapes, label tapes, containers, or the like. They can be applied in any conventional manner such as by spraying, by saturation, e.g. dipping the paper into the latex, by coating, and the like. The latexes can further be applied to variously formed materials, be they paper, synthetic fibers such as polyesters, polypropylenes, rayon, nylons, to masking tapes, to carpets, and the like. Another desired area of use is on various nonwoven textiles. Specific examples include mats, various hospital disposable products such as face masks, gowns, gloves, and the like, as well as commercial applications wherever mats are utilized such as in diapers, and the like. A preferred use is in the application of paper since it has been found that the latexes of the present invention unexpectedly improved cure rate development.
Once the latexes of the present invention have been applied to a substrate, they can be cured. Curing generally occurs by heating at a temperature of from about 25° C. to about 180° C. and preferably from about 100° C. to about 150° C. Curing can occur as in the presence of a heating means, for example an oven, an electronbeam, infrared heat, or at ambient temperature, or the like.
According to the present invention, the use of two functional monomers, that is an activatable ester monomer and either an acrylamide type monomer, a methacrylamide type monomer, a vinyl ether type monomer, or a carboxylic acid type monomer, or combinations thereof, has been found to generally result in a quicker cure time and/or a lower cure temperature when utilized with the various latex monomers. This is desirable since quicker or faster crosslinking times are useful. Thus, when the results of Example 1 are plotted, as in FIG. 1, it is seen that the initial cure strength, that is the wet tensile strength, is much greater for compounds of the present invention containing an activatable ester as well as a second functional containing monomer, for example acrylic acid. Cure time is very important in the utilization of latexes in that short heating times are highly desirable. For example, in the application of coatings to cellulosic material such as towels, quick cure times are desired. Example 1, as well as FIG. 2, also reveals that improved wet strengths are obtained utilizing a second functional monomer. That is at all cure times, large absolute improvement values in the wet tensile strength are obtained. Considering Example 2 as well as FIG. 2, it is once again apparent that utilization of a second functional monomer such as acrylamide yields great improvements in the initial cure time, that is the initial slope of the various curves. More importantly, as set forth in Example 2, dramatic improvements in the wet tensile strength are obtained and thereby conclusively proving that a synergistic result is obtained.
In general, use of the second or more functional type monomers results in an absolute value increase in the wet tensile strength at generally any given cure time. For example,.at 300 seconds of at least 1.5, desirably 2.0, and preferably 2.5 lbs/in.
The invention will be better understood by reference to the following examples.
The test method utilized in the examples for measuring wet tensile strength is as follows:
Whatman #4 chromatographic paper die-cut to 8"×10" is used with a tolerance of ±5.0% in an untreated weight basis. The sheets are saturated with the latex using a laboratory padder at a binder add-on target of 20±1.5% based on the finished sheet weight. The saturated sheets are air dried at room temperature and then duplicate sheets are cured on the steam heated drier cans at 315° F. for 15, 30, 60, and 300 seconds. All sheets are conditioned in accordance with TAPPI test method T402 before testing. Then they are immersed in distilled water until they are completely wetted. The tensile is then determined on four test strips in both the machine direction (MD) and in the cross direction (CD) for each cured sheet. The average of the eight results in each direction and the total tensile is reported as the sum of the CD and MD averages. This result is normalized to a basic weight of 73.0 lbs./300 ft. and a binder add on of 20%.
EXAMPLE I
Bottle scale polymertzations were carried out using the ingredients set forth below. In each case an initial charge was made to the bottles using the ingredients in the order listed in the table. The bottles were flushed with nitrogen, capped, and allowed to react 45 minutes at 65° C.
The bottles were opened, recharged with the appropriate amount of styrene, Sulfole 120 and butadiene, as listed in the table. This charge was reacted until the bottles were under vacuum as a result of most of the monomers having reacted. The bottles were opened a second time and further monomers, Sulfole 120, MAGME, and other cofunctional monomers added, as listed. This charge was also reacted to vacuum. The latexes obtained were tested without stripping. Some latexes were tested at the pH of the finished latex while others were tested at a pH of about 7.5 after adjustment with ammonium hydroxide.
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LATEX                                                                     
               A  B  C  D  E  F  G  H                                     
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INITIAL CHARGE                                                            
Water, ml      68 68 68 68 68 68 68 68                                    
Solution A, ml 40 40 40 40 0  0  0  0                                     
Solution B, ml 0  0  0  0  40 40 40 40                                    
Solution C, ml 60 60 60 60 60 60 60 60                                    
Solution D, ml 18 18 18 18 18 18 18 18                                    
Styrene, gms   15 15 15 15 15 15 15 15                                    
Reacted 45 minutes @ 65° C.                                        
FIRST CHARGE BACK                                                         
Styrene, gms   36 36 40 36 38 34 35 34                                    
Solution E, gms                                                           
               10 10 10 10 10 10 10 10                                    
Butadiene, gms 40 40 40 40 40 40 40 40                                    
Reacted to vacuum                                                         
SECOND CHARGE BACK                                                        
Water, ml      0  0  42 8  40 6  29 13                                    
Solution F, ml 53 53 11 53 11 53 53 53                                    
Solution D, ml 10 10 10 10 10 10 10 10                                    
Solution G, gms                                                           
               0  0  0  0  4  4  0  0                                     
Hydroxyethyl   0  0  0  0  0  0  2  4                                     
Acrylate, gms                                                             
Styrene, gms   36 18 40 36 38 34 35 34                                    
Solution E, gms                                                           
               10 10 10 10 10 10 10 10                                    
Solution H, gms                                                           
               0  20 0  0  0  0  0  0                                     
Butadiene, gms 40 40 40 40 40 40 40 40                                    
Reacted to Vacuum                                                         
Solution A -  0.4% (weight/volume i.e., W/V)                              
Dowfax 2A-1, 2.5% -                                                       
              (W/V) Sipex BOS,                                            
              1.5% (W/V) Aerosol MA, and 0.25%                            
              (W/V) Sequestrene Na-3 in deionized                         
              water.                                                      
Solution B -  Same as A except 0.425% (W/V) Dowfax                        
              2A-1                                                        
Solutlon C -  5.0% (W/V) itaconic acid in deionized                       
              water                                                       
Solution D -  5.0% (W/V) sodium persulfate in                             
              deionized water                                             
Solution E -  3.8% (W/V) Sulfole 120 in styrene                           
Solution F -  18.9% (W/V) MAGME in deionized water                        
Solution G -  50% (W/W) acrylamide in deionized water                     
Solution H -  20% (W/W) acrylic acid in styrene                           
LATEX PROPERTIES                                                          
               A  B  C  D  E  F  G  H                                     
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Total Solids, %                                                           
               44.9                                                       
                  44.1                                                    
                     44.6                                                 
                        44.3                                              
                           44.4                                           
                              44.1                                        
                                 45.0                                     
                                    44.6                                  
pH             2.3                                                        
                  2.2                                                     
                     2.5                                                  
                        2.2                                               
                           2.6                                            
                              2.2                                         
                                 2.2                                      
                                    2.1                                   
Brookfield     27 29 27 30 27 42 35 36                                    
Viscosity, cps.                                                           
Surface Tension,                                                          
               45.7                                                       
                  44.7                                                    
                     49.7                                                 
                        44.6                                              
                           47.1                                           
                              44.3                                        
                                 42.8                                     
                                    42.8                                  
dynes/cm                                                                  
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Latexes A and B of the bottle scale series relate to the use of MAGME in combination with acrylic acid and the use of itaconic acid in the initial step. These latexes both had 5 parts of MAGME and 0 and 2 parts respectively of acrylic acid.
Both latexes were tested in the Whatman #4 paper without steam stripping but with the pH adjusted to 7.5 by ammonium hydroxide. Latex B was also tested at 2.5 pH before adjustment. Results for total wet tensile strength were as follows:
______________________________________                                    
A              B           B                                              
(Control)      (Acrylic Acid)                                             
                           (Acrylic Acid)                                 
______________________________________                                    
pH      7.5        7.5         2.5                                        
Cure Time,                                                                
Secs.                                                                     
 15     22.3       25.0        26.9                                       
 30     26.9       27.0        30.1                                       
 60     28.7       30.4        29.9                                       
300     31.9       34.1        29.6                                       
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It is evident that Latex B which contains both acrylic acid and MAGME is better than Latex A which contains only MAGME. Not only did both "B" examples have a faster cure rate, but a higher wet tensile strength was also obtained. Thus, synergistic results were obtained.
EXAMPLE 2
Latexes C, D, E, and F of the bottle series illustrate the, use of acrylamide with MAGME and the synergistic effect thereof. Test results for total wet tensiles of Whatman #4 paper saturated with these latexes at low pH are as follows:
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Latex          C      D         E    F                                    
______________________________________                                    
MAGME, PHM     1      5         1    5                                    
Acrylamide, PHM                                                           
               0      0         1    1                                    
Cure Time,                                                                
Secs.          Total Wet Tensiles                                         
 15            16.9   25.0      18.3 33.0                                 
 30            18.2   26.1      21.1 33.8                                 
 60            19.8   27.6      22.3 32.8                                 
300            19.4   27.7      25.5 30.9                                 
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It is apparent from the above that increases in either MAGME or acrylamide (when the other is held constant) yield improved wet tensile strengths and increased cure rates at low cure times. For example, at 15 seconds and no acrylamide (C and D) increasing the MAGME from 1 to 5 parts increases the wet tensile (25.0-16.9)=8.1 units. Increasing the acrylamide from 0 to 1 part (C and E) increases the wet tensile at 15 second cure (18.3-16.9)+1.4 units. However, increasing both MAGME and acrylamide (C compared with E) results in an improvement (33.0-19.4) of 13.6 units which is much more than the sum of the individual (8.1+1.4 =9.5) effects and hence a synergistic result.
EXAMPLE 3
This example relates to the fact that a single anionic surfactant, Aerosol MA, can also be used to produce latexes. The latexes were prepared in bottles using 0.78 PHM of Aerosol MA-80 as the only surfactant.
Properties of the latexes were:
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           I          J      K                                            
______________________________________                                    
MAGME        3.5          5.0    5.0                                      
Acrylic Acid 0            2      0                                        
Acrylamide   2            0      2                                        
Coagulum,    0.4          0.4    0.4                                      
wet gms, %                                                                
pH           2.2          2.1    2.1                                      
Total Solids, %                                                           
             39.9         39.9   40.8                                     
Viscosity    18           18     18                                       
Surface      38.9         38.9   38.9                                     
Tension,                                                                  
dynes/cm                                                                  
______________________________________
EXAMPLE 4
This example relates to the preparation of latexes in bottles using a cationic system. The ingredients and latex properties are set forth in the following table:
______________________________________                                    
LATEXES                                                                   
           L    M       N      O    P     Q                               
______________________________________                                    
INITIAL CHARGE                                                            
Water, Ml    64     64      64   64   64    64                            
Solution A, ml                                                            
             40     40      40   40   40    40                            
Solution B, ml                                                            
             15     15      15   15   15    15                            
Solution C, ml                                                            
             8      8       8    8    8     8                             
Solution D, ml                                                            
             40     40      40   40   40    40                            
Solution E, ml                                                            
             8      8       8    8    8     8                             
Styrene, gm  15     15      15   15   15    15                            
Reacted 45 minutes @                                                      
65° C.                                                             
Solution F, ml                                                            
             8      8       8    8    8     8                             
Styrene, gms 31     29      30   28   29    27                            
Solution G, gms                                                           
             10     10      10   10   10    16                            
Solution E, gms                                                           
             4      4       4    4    4     4                             
Butadiene    40     40      40   40   40    40                            
Reacted to Vacuum                                                         
SECOND CHARGE                                                             
BACK                                                                      
Water, ml    29     4       27   2    25    0                             
Solution F, ml                                                            
             8      8       8    8    8     8                             
Solution H, ml                                                            
             40     67      40   67   40    67                            
50% acrylamide, gms                                                       
             0      0       4    4    8     8                             
Styrene, gms 27     25      26   24   25    23                            
Solution G, mgs                                                           
             10     10      10   10   10    10                            
Solution E, mgs                                                           
             8      8       8    8    8     8                             
Butadiene, gms                                                            
             40     40      40   40   40    40                            
Raised temperature                                                        
to 170° F. and                                                     
reacted to vacuum.                                                        
70% t-butyl  0.4    0       0.4  0    0.4   0.4                           
hydroperoxide, gms                                                        
Solution A -                                                              
          7.0% (W/V) Arquad C-33 in deionized water                       
Solution B -                                                              
          4.8% (W/V) aluminum chloride - hexahydrate                      
          in water                                                        
Solution C -                                                              
          5.0% (W/V) sodium chlorlde in water                             
Solution D -                                                              
          7.5% (W/V) Sipomer Q-5-80 in water                              
Solution E -                                                              
          3.5% (W/V) t-butyl hydroperoxide in styrene                     
Solution F -                                                              
          12.5% (W/V) Arquad C-33 in water                                
Solution G -                                                              
          3.75% (W/V) Sulfole 120 in styrene                              
Solution H -                                                              
          15.0% (W/V) MAGME In water                                      
LATEXES PROPERTIES                                                        
           L    M       N      O    P     Q                               
______________________________________                                    
Total Solids, %                                                           
             43.4   41.8    43.5 42.0 43.2  41.0                          
pH           2.3    2.1     2.4  2.1  2.4   2.4                           
Viscosity    19     21      21   20   32    18                            
Surface Tension                                                           
             39.9   45.7    43.8 42.8 40.9  39.9                          
______________________________________
All latexes were essentially coagulum free.
______________________________________                                    
CHEMICAL DEFINITIONS:                                                     
______________________________________                                    
MAGME    Methyl acrylamidoglycolate methyl ether                          
         CH.sub.2 = CH--CONHCHOCH.sub.3 FOOCH.sub.3                       
         American Cyanamid Company                                        
Sequestrene                                                               
         Trisodium ethylene diamine tetra acetate                         
Na-3     dihydrate.                                                       
         Ciba-Geigy Corp.                                                 
Aerosol MA                                                                
         Bis(1-methylamyl) sodium sulfosuccinate                          
         American Cyanamid Co. an anionic surfactant.                     
         80% in water.                                                    
Sipex BOS                                                                 
         Sodium 2-ethyl hexyl sulfate                                     
         Alcolac Inc. 40% aqueous solution.                               
Sulfole 120                                                               
         t-dodecyl mercaptan, avg. mol. wt. 198 Calc.                     
         purity wt. 96.8%                                                 
         and mercaptan sulfur wt. 15.4%                                   
         Phillips Petroleum Co., Rubber Division                          
Arquad C-33                                                               
         Trimethyl cocoammonium chloride                                  
         Armak Co. - 33% aqueous solution.                                
Sipomer  Dimethyl sulfate quarternary of                                  
Q-5-80   dimethylamino-ethyl methacrylate                                 
         CH.sub.2 = C(CH.sub.3)COOCH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3).sub
         .3 CH.sub.2 OSO.sub.3                                            
         80% aqueous solution. Alcolac, Inc.                              
______________________________________
While in accordance with the patent statutes, a best mode and preferred embodiment has been set forth in detail, the scope of the present invention is limited by the scope of the attached claims.

Claims (16)

What is claimed is:
1. A cellulosic material, comprising:
the cellulosic material, said cellulosic material containing a cured emulsion copolymer in the form of a solid, the copolymer made from an effective amount of (1) at least one latex forming monomer and (2) at least one functional type monomer having an activatable ester group which enables said copolymer to be crosslinked and a vinyl group with (3) at least one other functional type monomer, wherein said latex forming monomer is a conjugated diene, or said conjugated diene and at least one different conjugated diene comonomer having from 4 to 8 carbon atoms, or a conjugated diene and a vinyl substituted aromatic comonomer having from 8 to 12 carbon atoms, or a vinyl ester having a 1 to 8 carbon atom alkyl ester portion, or said vinyl ester and at least one ester of unsaturated mono or dicarboxylic acid comonomer having from 2 to 12 carbon atoms, or an ethylene monomer, or said ethylene and a vinyl chloride comonomer, or ethylene and a vinyl ester comonomer having from a 1 to 8 carbon atom alkyl ester portion, and wherein said other type functional monomer is an acrylamide or a 1 to 2 carbon atom alkyl derivative thereof, a methacrylamide or a 1 to 2 carbon atom alkyl derivative thereof, or combinations thereof.
2. A cellulosic material according to claim 1, wherein the amount of said latex forming monomer is from about 85 percent to about 99.5 percent by weight based upon the weight of said total monomers, wherein the amount of said two or more different functional monomers is from about 0.5 percent to about 15 percent by weight based upon the weight of said total monomers, is a conjugated diene, or said conjugated diene and, a vinyl ester, or said vinyl ester and, or an ethylene monomer, or said ethylene and.
3. A cellulosic material according to claim 2, wherein said conjugated diene has from 4 to 8 carbon atoms, wherein said conjugated diene comonomer is a different conjugated diene monomer, a vinyl substituted aromatic monomer, or combinations thereof, wherein said different conjugated diene has from 4 to 8 carbon atoms, wherein said vinyl substituted aromatic monomet has from 8 to 12 carbon atoms,
wherein said vinyl ester has a 1 to 8 carbon atom alkyl ester portion, wherein said vinyl ester comonomer is ethylene, an ester of a mono or a dicarboxylic acid, or combinations thereof, wherein said ester portion of said mono or said dicarboxylic acid is an alkyl having from 2 to 12 carbon atoms,
wherein said ethylene comonomer is vinyl chloride, a vinyl ester, or combinations thereof, wherein said vinyl ester comonomer has a 1 to 8 carbon atom alkyl ester portion;
wherein said vinyl containing ester activatable monomer is
methyl acrylamidoglycolate (MAC)
ethyl acrylamidoclycolate (EAG)
butyl acrylamidoglycolate (BAG)
methyl acrylamidoglycolate methyl ether (MAGEE)
butyl acrylamidoglycolate butyl ether (BAGBE)
methyl methacryloxyacetate
ethyl acrylamido-N-oxalate (N-ethyloxalyl acrylamide)
N,N'-bis(ethyloxalyl)acrylamide
N-isopropyl-N-ethyloxalyl-3-propylamino methacrylamide
N-ethyloxalyl-N'-methyleneaminoacrylamide
ethyl N-2-ethyloxamatoacrylate
ethyl 3-pyruvylacrylate
ethyl methylenepyruvate
methyl acrylthiocarbonyloxyacetate (Methyl thiacryloxyacetate)
methyl thiacrylthioglycolate
methyl acryl-2-thioglycolate
methyl thiacrylamidoacetate
methyl acrylamidoglycolate thioether
methyl acrylamido-N-methylenethioglycolate, or
p-ethyl oxalyl styrene.
4. A cellulosic material according to claim 3, wherein the amount of said latex forming monomer is from about 94 percent to about 97 percent by weight, wherein the total amount of said two or more functional monomers is from about 3 percent to about 6 percent by weight, wherein said copolymer is free-radically polymerized, wherein said latex monomer is butadiene, butadiene and styrene, vinyl acetate, ethylene and vinyl acetate, or ethylene and vinyl chloride, wherein one type of said functional monomer is acrylamide, methacrylamide, or combinations thereof, and wherein said functional activatable ester monomer is methylacrylamidoglycolate, methylacrylamidoglycolate methyl ether, or combinations thereof.
5. A non-woven textile, comprising:
the non-woven textile, said non-woven textile containing a cured emulsion copolymer in the form of a solid, the copolymer made from an effective amount of (1) at least one latex forming monomer and (2) at least one functional type monomer having an activatable ester group which enables said copolymer to be crosslinked and a vinyl group with (3) at least one other functional type monomer, wherein said latex forming monomer is a conjugated diene, or said conjugated diene and at least one different conjugated diene comonomer having from 4 to 8 carbon atoms, or a conjugated diene and a vinyl substituted aromatic comonomer having from 8 to 12 carbon atoms, or a vinyl ester having a 1 to 8 carbon atom alkyl ester portion, or said vinyl ester and at least one ester of an unsaturated mono or dicarboxylic acid comonomer having from 2 to 12 carbon atoms, or an ethylene monomer, or said ethylene and a vinyl chloride comonomer, or ethylene and a vinyl ester comonomer having from a 1 to 8 carbon atom alkyl ester portion and wherein said other type functional monomer is an acrylamide or a 1 to 2 carbon atom alkyl derivative thereof, a methacrylamide or a 1 to 2 carbon atom alkyl derivative thereof, or combinations thereof.
6. A non-woven textile according to claim 5, wherein the amount of said latex forming monomer is from about 85 percent to about 99.5 percent by weight based upon the weight of said total monomers, wherein the amount of said two or more different functional monomers is from about 0.5 percent to about 15 percent by weight based upon the weight of said total monomers, forming monomer is a conjugated diene, or said conjugated diene and, a vinyl ester, or said vinyl ester and, or an ethylene monomer, or said ethylene and.
7. A non-woven textile according to claim 6, wherein said conjugated diene has from 4 to 8 carbon atoms, wherein said conjugated diene comonomer is a different conjugated diene monomer, a vinyl substituted aromatic monomer, or combinations thereof, wherein said different conjugated diene has from 4 to 8 carbon atoms, wherein said vinyl substituted aromatic monomer has from 8 to 12 carbon atoms,
wherein said vinyl ester has a 1 to 8 carbon atom alkyl ester portion, wherein said vinyl ester comonomer is ethylene, an ester of a mono or a dicarboxylic acid, or combinations thereof, wherein said ester portion of said mono or said dicarboxylic acid is an alkyl having from 2 to 12 carbon atoms,
wherein said ethylene comonomer is vinyl chloride, a vinyl ester, or combinations thereof, wherein said vinyl ester comonomer has a 1 to 8 carbon atom alkyl ester portion;
wherein said vinyl containing ester activatable monomer is
methyl acrylamidoglycolate (MAG)
ethyl acrylamidoclycolate (EAG)
butyl acrylamidoglycolate (BAG)
methyl acrylamidoglycolate methyl ether (MAGEE)
butyl acrylamidoglycolate butyl ether (BAGBE)
methyl methacryloxyacetate
ethyl acrylamido-N-oxalate (N-ethyloxalyl acrylamide)
N,N'-bis(ethyloxalyl)acrylamide
N-isopropyl-N-ethyloxalyl-3-propylamino methacrylamide
N-ethyloxalyl-N'-methyleneaminoacrylamide
ethyl N-2-ethyloxamatoacrylate
ethyl 3-pyruvylacrylate
ethyl methylenepyruvate
methyl acrylthiocarbonyloxyacetate (methylthiacryloxyacetate)
methyl thiacrylthioglycolate
methyl acryl-2-thioglycolate
methyl thiacrylamidoacetate
methyl acrylamidoglycolate thioether
methyl acrylamido-N-methylenethioglycolate, or
p-ethyl oxalyl styrene.
8. A non-woven textile according to claim 7, wherein the amount of said latex forming monomer is from about 94 percent to about 97 percent by weight, wherein the total amount of said two or more functional monomers is from about 3 percent to about 6 percent by weight, wherein said copolymer is free-radically polymerized, wherein said latex monomer is butadiene, butadiene and styrene, or vinyl acetate, ethylene and vinyl acetate, or ethylene and vinyl chloride, wherein one type of said functional monomer is acrylamide, methacrylamide, or combinations thereof, and wherein said functional activatable ester monomer is methylacrylamidoglycolate, methylacrylamidoglycolate methyl ether, or combinations thereof.
9. A non-woven textile substrate or a cellulosic substrate containing a cured emulsion copolymer of a latex, comprising:
the non-woven textile substrate or the cellulosic substrate, the cured emulsion copolymer of a latex applied to said non-woven textile or said cellulosic substrate, said cured emulsion copolymer in the form of a solid, the emulsion copolymer made by polymerizing (1) at least one latex forming monomer and (2) at least one functional type monomer having an activatable ester group which enables said copolymer to be crosslinked and a vinyl group with (3) at least one other functional type monomer, wherein said latex forming monomer is a conjugated diene, or said conjugated diene and at least one different conjugated diene comonomer having from 4 to 8 carbon atoms, or a conjugated diene and a vinyl substituted aromatic comonomer having from 8 to 12 carbon atoms, or a vinyl ester having a 1 to 8 carbon atom alkyl ester portion, or said vinyl ester and at least one ester of am unsaturated mono or dicarboxylic acid comonomer having from 2 to 12 carbon atoms, or an ethylene monomer, or said ethylene and a vinyl chloride comonomer, or ethylene and a vinyl ester comonomer having from a 1 to 8 carbon atom alkyl ester portion, wherein the amount of said functional monomers is from 0.5 percent to about 15 percent by weight based upon the weight of said total monomers,
wherein the amount of said latex forming monomer is from about 85 percent to about 99.5 percent by weight based upon the weight of said total monomers,
wherein the pH of said latex is from about 2.0 to about 7.0,
and wherein said other type functional monomer is an acrylamide or a 1 to 2 carbon atom alkyl derivative thereof; a methacrylamide or a 1 to 2 carbon atom alkyl derivative thereof; or combinations thereof.
10. A composition according to claim 9, wherein said latex contains from about 10 percent to about 60 percent by weight of said copolymer solids,
wherein said conjugated diene comonomer is selected from the group consisting of a different conjugated diene, a vinyl substituted aromatic, or combinations thereof, wherein said different conjugated diene has from 4 to 8 carbon atoms, wherein said vinyl substituted aromatic has from 8 to 12 carbon atoms,
wherein said vinyl ester has a 1 to 8 carbon atom alkyl ester portion, wherein said vinyl ester comonomer is selected from the group consisting of ethylene, an ester of a mono or a dicarboxylic acid, or combinations thereof, wherein said ester of said mono or said dicarboxylic acid has from 2 to 12 carbon atoms;
wherein said ethylene comonomer is vinyl chloride, or a vinyl ester, or combinations thereof, wherein said vinyl ester comonomer has a 1 to 8 carbon atom alkyl ester portion, and
wherein said acrylamide type functional monomer is acrylamide or an alkyl derivative thereof having from 1 or 2 carbon atoms attached to either the nitrogen atom, said vinyl group, or both, wherein the methacrylamide type monomer is methacrylamide, or an alkyl derivative thereof having 1 or 2 carbon atoms attached to either the nitrogen atom, the vinyl group, or both.
11. A composition according to claim 10, wherein the amount of said solids in said latex is from about 40 percent to about 55 percent by weight, wherein said conjugated diene and said different diene has from 4 to 6 carbon atoms, wherein the amount of said vinyl substituted aromatic comonomer is from about 0 percent to about 70 percent by weight and wherein the amount of said conjugated diene comonomer is from 1 percent to 99 percent by weight based upon the total weight of the latex forming monomers;
wherein said vinyl ester has a 1 to 5 carbon alkyl ester portion, wherein the amount of said ethylene comonomer is from about 10 percent to about 95 percent by weight based upon the weight of the latex forming monomers, and wherein said ester of said mono or said dicarboxylic acid comonomer is from about 5 percent to about 50 percent by weight based upon the total weight of the latex forming monomers,
wherein said ethylene comonomer is vinyl chloride in the amount of from about 5 percent to about 40 percent by weight based upon the total weight of the total monomers, or wherein said ethylene comonomer is a vinyl ester having a 1 to 5 carbon atoms alkyl ester portion, and wherein the amount of said vinyl ester comonomer is from about 5 percent to about 90 percent by weight based upon the total weight of the latex forming monomers,
wherein the pH of said latex is from about 2.0 to about 4.0, wherein the amount of said functional monomers is from about 1 percent to about 10 percent by weight,
wherein the amount of said latex forming monomer is from about 90 percent to about 99 percent by weight,
and wherein said activatable ester monomer is
methyl acrylamidoglycolate (MAG)
ethyl acrylamidoclycolate (EAG)
butyl acrylamidoglycolate (BAG)
methyl acrylamidoglycolate methyl ether (MAGME)
butyl acrylamidoglycolate butyl ether (BAGBE)
methyl methacryloxyacetate
ethyl acrylamido-N-oxalate (N-ethyloxalyl acrylamide)
N,N'-bis(ethyloxalyl)acrylamide
N-isopropyl-N-ethyloxalyl-3-propylamino methacrylamide
N-ethyloxalyl-N'-methyleneaminoacrylamide
ethyl N-2-ethyloxamatoacrylate
ethyl 3-pyruvylacrylate
ethyl methylenepyruvate
methyl acrylthiocarbonyloxyacetate (Methyl thiacryloxyacetate)
methyl thiacrylthioglycolate
methyl acryl-2-thioglycolate
methyl thiacrylamidoacetate
methyl acrylamidoglycolate thioether
methyl acrylamido-N-methylenethioglycolate, or
p-ethyl oxalyl styrene.
12. A composition according to claim 11, wherein said copolymer is free-radically polymerized,
wherein said latex forming monomer is butadiene, butadiene and styrene, vinyl acetate, ethylene and vinyl acetate, ethylene and vinyl chloride, or combinations thereof,
wherein said remaining functional monomer is acrylamide, or methacrylamide, and
wherein said functional activatable ester is methacrylamidoglycolate, methylacrylamidoglycolate methyl ether, butylacrylamidoglycolate, butylacrylamidoglycolate butyl ether, or combinations thereof.
13. A coated cellulosic material containing a cured emulsion copolymer of a latex, comprising:
the cellulosic material, the cured emulsion copolymer of a latex coating said cellulosic material, said cured emulsion copolymer being in the form of a solid, the emulsion copolymer made by polymerizing (1) at least one latex forming monomer and (2) at least one functional type monomer having an activatable ester group which enables said copolymer to be crosslinked and a vinyl group with (3) at least one other functional type monomer, wherein said latex forming monomer is a conjugated diene, or said conjugated diene and at least one different conjugated diene comonomer having from 4 to 8 carbon atoms, or a conjugated diene and a vinyl substituted aromatic comonomer having from 8 to 12 carbon atoms, or a vinyl ester having a 1 to 8 carbon atom alkyl ester portion, or said vinyl ester and at least one ester of an unsaturated mono or dicarboxylic acid comonomer having from 2 to 12 carbon atoms, or an ethylene monomer, or said ethylene and a vinyl chloride comonomer, or ethylene and a vinyl ester comonomer having from a 1 to 8 carbon atom alkyl ester portion, wherein the amount of said functional monomers is from 0.5 percent to about 15 percent by weight based upon the weight of said total monomers,
wherein the amount of said latex forming monomer is from about 85 percent to about 99.5 percent by weight based upon the weight of said total monomers,
wherein the pH of said latex is from about 2.0 to about 7.0,
and wherein said other type functional monomer is an acrylamide or a 1 to 2 carbon atom alkyl derivative thereof; a methacrylamide or a 1 to 2 carbon atom alkyl derivative thereof; or combinations thereof.
14. A coated cellulosic material according to claim 13, wherein said latex contains from about 10 percent to about 60 percent by weight of said copolymer solids,
wherein said conjugated diene comonomer is selected from the group consisting of a different conjugated diene, a vinyl substituted aromatic, or combinations thereof, wherein said different conjugated diene has from 4 to 8 carbon atoms, wherein said vinyl substituted aromatic has from 8 to 12 carbon atoms,
wherein said vinyl ester has a 1 to 8 carbon atom alkyl ester portion, wherein said vinyl ester comonomer is selected from the group consisting of ethylene, an ester of a mono or a dicarboxylic acid, or combinations thereof, wherein said ester of said mono or said dicarboxylic acid has from 2 to 12 carbon atoms;
wherein said ethylene comonomer is vinyl chloride, or a vinyl ester, or combinations thereof, wherein said vinyl ester comonomer has a 1 to 8 carbon atom alkyl ester portion, and
wherein said acrylamide type functional monomer is acrylamide or an alkyl derivative thereof having from 1 or 2 carbon atoms attached to either the nitrogen atom, said vinyl group, or both, wherein the methacrylamide type monomer is methacrylamide, or an alkyl derivative thereof having 1 or 2 carbon atoms attached to either the nitrogen atom, the vinyl group, or both.
15. A coated cellulosic material according to claim 14, wherein the amount of said solids in said latex is from about 40 percent to about 55 percent by weight, wherein said conjugated diene and said different diene has from 4 to 6 carbon atoms, wherein the amount of said vinyl substituted aromatic comonomer is from about 0 percent to about 70 percent by weight and wherein the amount of said conjugated diene comonomer is from 1 percent to 99 percent by weight based upon the total weight of the latex forming monomers;
wherein said vinyl ester has a 1 to 5 carbon alkyl ester portion, wherein the amount of said ethylene comonomer is from about 10 percent to about 95 percent by weight based upon the weight of the latex forming monomers, and wherein said ester of said mono or said dicarboxylic acid comonomer is from about 5 percent to about 50 percent by weight based upon the total weight of the latex forming monomers,
wherein said ethylene comonomer is vinyl chloride in the amount of from about 5 percent to about 40 percent by weight based upon the total weight of the total monomers, or wherein said ethylene comonomer is a vinyl ester having a 1 to 5 carbon atoms alkyl ester portion, and wherein the amount of said vinyl ester comonomer is from about 5 percent to about 90 percent by weight based upon the total weight of the latex forming monomers,
wherein the pH of said latex is from about 2.0 to about 4.0, wherein the amount of said functional monomers is from about 1 percent to about 10 percent by weight,
wherein the amount of said latex forming monomer is from about 90 percent to about 99 percent by weight,
and wherein said activatable ester monomer is
methyl acrylamidoglycolate (MAC)
ethyl acrylamidoclycolate (EAG)
butyl acrylamidoglycolate (BAG)
methyl acrylamidoglycolate methyl ether (MAGME)
butyl acrylamidoglycolate butyl ether (BAGBE)
methyl methacryloxyacetate
ethyl acrylamido-N-oxalate (N-ethyloxalyl acrylamide)
N,N'-bis(ethyloxalyl)acrylamide
N-isopropyl-N-ethyloxalyl-3-propylamino methacrylamide
N-ethyloxalyl-N'-methyleneaminoacrylamide
ethyl N-2-ethyloxamatoacrylate
ethyl 3-pyruvylacrylate
ethyl methylenepyruvate
methyl acrylthiocarbonyloxyacetate (Methyl thiacryloxyacetate)
methyl thiacrylthioglycolate
methyl acryl-2-thioglycolate
methyl thiacrylamidoacetate
methyl acrylamidoglycolate thioether
methyl acrylamido-N-methylenethioglycolate, or
p-ethyl oxalyl styrene.
16. A coated cellulosic material according to claim 15, wherein said copolymer is free-radically polymerized,
wherein said latex forming monomer is butadiene, butadiene and styrene, vinyl acetate, ethylene and vinyl acetate, ethylene and vinyl chloride, or combinations thereof,
wherein said remaining functional monomer is acrylamide, or methacrylamide, and
wherein said functional activatable ester is methacrylamidoglycolate, methylacrylamidoglycolate methyl ether, butylacrylamidoglycolate, butylacrylamidoglycolate butyl ether, or combinations thereof.
US07/150,601 1986-04-03 1988-02-01 Latex containing copolymers having a plurality of activatable functional ester groups therein Expired - Fee Related US5478641A (en)

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